Carbon Dioxide Activation by Alkaline-Earth Metals: Formation and Spectroscopic Characterization of OCMCO3 and MC2O4 (M = Ca, Sr, Ba) in Solid Neon.

The reactions of alkaline-earth metal atoms (Ca, Sr, and Ba) with carbon dioxide are investigated using matrix isolation infrared spectroscopy in solid neon. The ground-state metal atoms react with two carbon dioxide molecules to produce the oxalate complexes MC2O4 and the carbonate-carbonyl complexes OCMCO3 (M = Ca, Sr, Ba) spontaneously on annealing. The species are identified by the effects of isotopic substitution on their infrared spectra as well as density functional calculations. Bonding analyses reveal that the attractive forces between M2+ and (CO3)2- or (C2O4)2- in the OCMCO3 and MC2O4 complexes come mainly from electrostatic attraction, but covalent orbital interactions also play an important role, which are dominated by the ligand-to-metal donation bonding. The calcium, strontium, and barium metal centers in these complexes use their ns and predominately (n - 1)d atomic orbitals for covalent bonding that mimic transition metals.

Generation and Characterization of the Charge-Transferred Diradical Complex CaCO2 with an Open-Shell Singlet Ground State.

The CaCO2 complex is generated via the reaction of excited-state calcium atom with carbon dioxide in a solid neon matrix. Infrared absorption spectroscopy and quantum chemical calculations reveal that the complex has a planar four-membered ring structure with a strongly bent CO2 ligand side-on coordinated to the calcium center in an η2-O, O manner. The complex has an open-shell singlet ground state, which can be described as the bonding interactions between a Ca+ (4s1) cation in the doublet ground state and a doublet ground state CO2- anion. The analysis of the bonding situation suggests that the Ca-O2C bonds have a large (75%) electrostatic character. The covalent (orbital) interactions come from the coupling of the unpaired electrons of Ca+ and CO2- giving rise to electron-sharing bonding and a stronger contribution from dative bonding (Ca+)←(CO2-). The atomic orbitals (AOs) of Ca+ that are engaged in the covalent bonds are the 4s AO for the electron-sharing bonds and the 3d AOs for the dative bonds. This is further evidence for the assignment of the heavier alkaline-earth atoms as transition metals rather than main-group elements.

Evaluation on the Seal Performance of SMP-Based Packers in Oil Wells.

Packers based on shape memory polymers (SMPs) are an emerging technology that have the advantages of compact structure, easy manufacture, and adaptability to complex wells. This paper proposes a finite element model to simulate the setting process and mechanical response of an SMP packer. The investigated material is an epoxy-based thermal responsive SMP, whose relaxation modulus and thermal expansion coefficient were measured at different temperatures. Based on the experimental data, the model describes the viscoelastic behavior of the SMP using the generalized Maxwell model. The results show that the SMP packer could provide sufficient contact stress under downhole conditions, even after the stress was relaxed. A further parametric study revealed that the most significant factor in sealing effects is the wellbore pressure, followed by the interference between the packer and the annular, the seal length, the pre-compression, and the setting temperature. High downhole pressures require more significant contact stress and increase the risk of slip between the packer and casing wall by promoting shear stress. Increasing the seal length and interference enhances the contact stress and mitigates the shear stress to improve the seal performance. Pre-compression and setting temperatures are minor factors that have little influence on sealability.

Naked-eye sensing and target-guiding treatment of bacterial infection using pH-tunable multicolor luminescent lanthanide-based hydrogel.

In this work, a pH-tunable multicolor luminescent lanthanide-based hydrogel (CS/DEX/CP) was prepared based on lanthanide coordination polymer (CP), dextran aldehyde (DEX) and chitosan (CS). The CP was obtained by the self-assembly of guanosine acid (GMP), ciprofloxacin (CIP), Eu3+, and Tb3+. As-prepared CS/DEX/CP hydrogel could emit blue, green, and red luminescence of CIP, Tb3+, and Eu3+, respectively. It was also found that the luminescence of CS/DEX/CP hydrogel exhibited visual color change in the pH range of 5.5 to 8. Such pH-sensitive hydrogel was multicolor-responsive to protons produced by bacterial growth, therefore, it could provide early warning of bacterial infection by naked-eye. In addition, the increased acidity resulted in not only the degradation of acid-labile Schiff base linkages between DEX and CS, but also the fracture of coordination between CIP and lanthanide ions. As a result, the released CIP and CS showed significantly antibacterial activity against both S. aureus and E. coli.

Key genes affecting the progression of nasopharyngeal carcinoma identified by RNA-sequencing and bioinformatic analysis.

BACKGROUND: The present work was conducted to screen the potential biomarkers affecting nasopharyngeal carcinoma (NPC) progression through RNA-sequencing (RNA-seq), bioinformatic analysis and functional experiments. MATERIALS AND METHODS: Six normal samples and five NPC clinical samples were collected for RNA-seq analysis. The expression levels in both groups were determined through student's t-test. We identified genes of P < 0.01 as the differentially expressed genes (DEGs). In addition, gene set enrichment analysis (GSEA) was conducted. Afterwards, STRING V10 database was employed to extract protein interactions among the DEGs. Later, we established a protein-protein interaction (PPI) network, and used the Cytoscape software for network visualization. qRT-PCR was conducted to verify hub genes from clinical samples. Then, the function of CXCL10 in cell proliferation, apoptosis, invasion and migration was evaluated. RESULTS: A total of 2024 DEGs were identified, among which, 1449 were down-regulated and 575 were up-regulated. The PPI was constructed, and the hub genes including Insulin Like Growth Factor 1 (IGF1), C-X-C Motif Chemokine Ligand 10 (CXCL10), Interleukin 13 (IL13), Intercellular Adhesion Molecule 1 (ICAM1), G Protein Subunit Gamma Transducin 1 (GNGT1), Matrix Metallopeptidase 1 (MMP1), Neurexin 1 (NRXN1) and Matrix Metallopeptidase 3 (MMP3) were obtained. The expression levels of CXCL10, IGF1, MMP3, MMP1, ICAM1, and IL-13 were significantly up-regulated in tumor tissues. High expression levels of CXCL10, MMP3 and ICAM1 predicted poor prognosis of NPC patients. CXCL10 silencing suppressed NPC cell proliferation and migration. CONCLUSIONS: CXCL10 may serve as a potential key gene affecting NPC genesis and progression.

Covalent Bonding Between Be+ and CO2 in BeOCO+ with a Surprisingly High Antisymmetric OCO Stretching Vibration.

The cationic complex BeOCO+ is produced in a solid neon matrix. Infrared absorption spectroscopic study shows that it has a very high antisymmetric OCO stretching vibration of 2418.9 cm-1, which is about 71 cm-1 blue-shifted from that of free CO2. The quantum chemical calculations are in very good agreement with the experimental observation. Depending on the theoretical method, a linear or quasi-linear structure is predicted for the cation. The analysis of the electronic structure shows that the bonding of Be+ to one oxygen atom induces very little charge migration between the two moieties, but it causes a significant change in the σ-charge distribution that strengthens the terminal C-O bond, leading to the observed blue shift. The bonding analysis reveals that the Be+ ← OCO donation results in strong binding due to the interference of the wave function and a charge polarization within the CO2 fragment and hybridization to Be+ but only negligible charge donation.

Molecular Markers of MDR of Chemotherapy for HSCC: Proteomic Screening With High-Throughput Liquid Chromatography-Tandem Mass Spectrometry.

BACKGROUND: Hypopharyngeal squamous cell cancer (HSCC) is a head and neck tumor with a poor prognosis. Chemotherapy lacks effectiveness because of multidrug resistance (MDR), which has increased toxic side effects. Thus, there is an urgent need to identify the molecular markers of MDR of chemotherapy for HSCC. METHODS: Fifty clinical samples of HSCC were derived from patients including 12 sensitive or resistant to chemotherapy drugs. Proteomic screening was performed using liquid chromatography-tandem mass spectrometry (LC-MS), which was based on data-independent acquisition. Molecular markers of MDR of chemotherapy in patients with HSCC were identified with clinical data and validated with ELISA. RESULTS: A total of 673 differentially expressed proteins were identified in HSCC samples, where 172 were upregulated and 501 were downregulated. A total of 183 differentially expressed proteins including 102 upregulated and 81 downregulated proteins, were identified by comparing cancer sensitive to chemotherapy with cancer resistant to chemotherapy. Clinical HSCC samples had significantly higher expression of FADD and significantly lower expression of RIPK1. Expressions of FADD and RIPK1 proteins were significantly lower in the chemotherapy-sensitive group. These expression differences were not correlated with clinical data. RIPK1 and FADD are involved in necroptosis and the signaling pathway of PRRs. Using ELISA, the low expression of RIPK1 and FADD was found in the patients sensitive to chemotherapy. CONCLUSION: LC-MS proteomics is an effective method to identify the molecular markers of HSCC. FADD and RIPK1 can act as molecular markers of MDR of chemotherapy in patients with HSCC and may function through necroptosis and the PRR signaling pathway.

Rice husk-derived biochar can aggravate arsenic mobility in ferrous-rich groundwater during oxygenation.

Elevated As(III) and Fe(II) in shallow reducing groundwater can be frequently re-oxidized by introducing O2 due to natural/anthropogenic processes, thus leading to oxidative precipitation of As as well as Fe. Nevertheless, the geochemical process may be impacted by co-existing engineered black carbon due to its considerable applications, which remains poorly understood. Taking rice husk-derived biochar prepared at 500 °C as an example, we explored its impact on the process particularly for the As(III) oxidation and (im)mobilization during the oxygenation. The presence of the biochar had a negligible effect on the As(III) oxidation and immobilization extents within 1 d, while accelerating their rates. However, the immobilized As(III) was significantly liberated from the formed Fe(III) minerals afterward within 21 d, which was 2.2-fold higher than that in the absence of the biochar. The enhanced As(III) liberation was attributed to the presence of the surface silicon-carbon structure, consisting of the outer silicon and inner carbon layers, of the rice husk-derived biochar. The outer silicon components, particularly for the dissolved silicate primarily promoted the As(III) release via ligand exchange, while significantly impeding the transformation of ferrihydrite to lepidocrocite and goethite still resulted secondarily in the As(III) release. Our findings reveal the possible impact of biochar on the environmental behavior and fate of As(III) in the Fe(II)-rich groundwater during the oxygenation. This work highlights that biochar, particularly for its structural features should be a concern in re-mobilizing As in such scenarios when the oxygenation time reaches several days or weeks.

Carboxymethyl chitosan‒promoted luminescence of lanthanide metallogel and its application in assay of multiple metal ions.

In this work, the luminescence of lanthanide supramolecular metallogel formed by the self-assembly of 5,5',5″-(1,3,5-triazine-2,4,6-triyl)tris(azanediyl)triisophthalate (H6L) and Tb3+ was efficiently promoted by carboxymethyl chitosan (CMCS). The total quantum yield of the resultant metallogel (denoted as H6L/Tb3+/CMCS gel) was 9 times higher than the gel without CMCS. The average lifetime of H6L/Tb3+/CMCS gel increased from 0.51 ms to 1.20 ms. More importantly, the aqueous dispersion of H6L/Tb3+/CMCS xerogels showed a stable and pH-dependent luminescence. Based on the selective affinity of CMCS to different metal ions as well as with the aid of principal component analysis, H6L/Tb3+ /CMCS can be used as a sensor array to distinguish 11 metal ions (P < 0.05). This work provides a new strategy for the design and development of bio-based functional luminescent lanthanide supramolecular metallogels.

Luminescence sensitization of terbium-loaded supramolecular gels by hydroxybenzoic acids and used for salicylates sensing.

The luminescent terbium (Tb3+)-loaded supramolecular gels were facilely prepared through the self-assembly of Fmoc-diphenylalanine (FmocPhePhe) at room temperature. Hydroxybenzoic acid (HA, the isomers are denoted as 2-HA, 3-HA, and 4-HA depending upon the positions of hydroxyl groups) was used as a sensitizer to Tb3+. The luminescence sensitization of Tb3+ in the gels was realized by the coordination with hydroxybenzoic acids. The spectra of luminescence, UV-vis, FT-IR, and 1H NMR verified that this sensitization was attributed to the energy transfer from hydroxybenzoic acids to Tb3+. The results of XRD, SEM, and phase transfer temperature further indicated that the initial molecule arrangement of the gels was significantly changed by 2-HA, resulting in more ordered and more compact morphology of the gels. 2-HA exhibited more effective sensitization to Tb3+ in the gels than 3-HA and 4-HA. It was also found that 2-HA did not affect the self-assembly of FmocPhePhe. Due to the effective fluorescence sensitization by 2-HA, the as-prepared gels can be used for salicylic acid sensing with 6.8 µM of the detection limit. This strategy has been successfully used for the detection of salicylates in pharmaceuticals and cosmetics.

Generation and Characterization of the C3 O2 - Anion with an Unexpected Unsymmetrical Structure.

The carbon suboxide anion C3 O2 - is generated in solid neon matrix. It is characterized by infrared absorption spectroscopy as well as quantum chemical calculations to have a planar Cs structure where two CO groups with significantly different bond lengths and angles are attached in a zigzag fashion to the central carbon atom. Bonding analysis indicates that it is best described by the bonding interactions between a neutral CO in a triplet excited state and a doublet excited state of CCO- .

CO-Induced Dinitrogen Fixation and Cleavage Mediated by Boron.

The boron atoms react with carbon monoxide and dinitrogen forming the end-on bonded NNBCO complex in solid neon or in nitrogen matrices. The NNBCO complex rearranges to the (η2 -N2 )BCO isomer with a more activated side-on bonded dinitrogen ligand upon visible light excitation. (η2 -N2 )BCO and its weakly CO-coordinated complexes further isomerize to the NBNCO and B(NCO)2 molecules with N-N bond being completely cleaved under UV light irradiation. The geometries, energies and vibrational spectra of the molecules are calculated with quantum chemical methods and the electronic structures are analyzed with charge- and energy-partitioning methods.

In Situ Assessment of Donghu Lake China Using Rare Minnow (Gobiocypris rarus).

In this work, rare minnow (Gobiocypris rarus) was applied as a sentinel organism and set in cages at control and test sampling sites in Donghu Lake for 4 weeks in March, June, September, and December 2016 to assess the biological toxicity of in situ water. Sampling for active biomonitoring and physicochemical variables was performed weekly. The control was obtained from the outdoor pool of the Institute of Hydrobiology, China. Superoxide dismutase, lipoperoxidation, metallothioneins, acetylcholinesterase activity, and Vtg mRNA expression were determined as biomarkers during the field exposure period. Survival and growth also were monitored to evaluate the overall physiological condition of the fish. The seasonal changes of organic pollutants and trace metals (As, Hg, Cr, Cu, Zn, Cd, Pb) in surface water were determined. The integrated biomarker response (IBR) index was applied to summarize biomarker responses and correlate stress levels with concentrations of organic pollutants and trace metals in the surface water. Results indicated that complex pollution by persistent organic pollutants and heavy metals was present in Donghu Lake and that the in situ exposed organisms were stressed. Moreover, the complex pollution of Donghu Lake in summer and autumn was more serious than that in spring and winter. Active biomonitoring combined with IBR analysis enabled good discrimination among different exposure seasons. The proposed protocol with caged rare minnow revealed marked biological effects caused by the investigated Lake and a useful approach that can easily be extended to monitor water pollution.

Multi-Responsive Lanthanide-Based Hydrogel with Encryption, Naked Eye Sensing, Shape Memory, Self-Healing, and Antibacterial Activity.

In this work, we reported a multi-responsive luminescent hydrogel with properties of encryption, naked eye sensing of glucose, shape memory, self-healing, and antibacterial activity. The hydrogel (GA/CCS/DNSA/Eu3+) was obtained by mixing phenylboronic acid-modified gelatin (GA-DBA), catechol-modified carboxymethyl chitosan (CCS-PCA), 3,5-dinitrosalicylic acid (DNSA), and Eu3+ ions through a facile heating-cooling process. The resultant hydrogel exhibits reversible luminescence and color and phase changes in response to temperature, acid/base, salt, and redox stimuli. Based on the multiple responsiveness, information encryption and decryption, naked eye sensing of glucose, remarkable shape memory, and enhanced mechanical properties of the as-prepared hydrogel were realized. In addition, the self-healing capacity was also achieved due to the dynamic bonds in GA/CCS/DNSA/Eu3+ hydrogels. Specifically, the GA/CCS/DNSA/Eu3+ hydrogels possess antibacterial activity owing to the bacteriostasis of the CCS-PCA and DNSA/Eu3+ complex. Thus, GA/CCS/DNSA/Eu3+ hydrogels have potential applications in the fields of anticounterfeiting, wearable devices, biomedicine, sensing, etc.

Determination of trace elements in high-purity quartz samples by ICP-OES and ICP-MS: A normal-pressure digestion pretreatment method for eliminating unfavorable substrate Si.

The analysis of siliceous matrix samples may adopt a two-step pretreatment, which includes melting with ammonium hydrogen fluoride and redissolving with nitric acid. However, the residual of substrate silicon unfavorable to the determination of trace elements in the samples due to serious matrix effects. Here, a new digestion method using simultaneously both ammonium bifluoride and nitric acid under normal pressure was developed for high-purity quartz sand sample. The digestion pretreatment is a two step process: melting/dissolving with both ammonium bifluoride and nitric acid at 200 °C for 2 h, and evaporating the solution at 250 °C to dryness. As confirmed by XRD analysis, silicates in the sample were converted to (NH4)3SiF6NO3 in the melting/dissolving step. TGA analysis shows that the generated (NH4)3SiF6NO3 could be decomposed and evaporated completely at 250 °C, which ensured a complete removal of silicon by the followed evaporation of the solution at 250 °C. As a result, the followed ICP-OES and ICP-MS analysis needed a solution dilution of only 100 times for the determination of Ca, Mg, Al, Rb, Ba, REE and other trace elements. The new method was applied to the analysis of three certified reference materials, and the results were well consistent with the standard value with RSD% values between 0.62% and 9.73%. Therefore, this method can be applied to the analysis of trace elements in high purity silica-based samples, with the advantages of time-saving, small dilution factor (only 100 times) and low detection limit.

A heat-set lanthanide metallogel capable of emitting stable luminescence under thermal, mechanical and water stimuli.

Preparing luminescence-stable lanthanide materials in a facile manner has always been an intriguing challenge. Herein we report an easy approach to the preparation of a heat-set lanthanide-based metallogel (H6L/Tb gel) with stable luminescence from 5,5',5''-(1,3,5-triazine-2,4,6-triyl)tris(azanediyl) triisophthalate (H6L) as a Tb3+ coordinating ligand. The heat-set H6L/Tb gel exhibits luminescence that mostly retains its intensity in the 0-90 °C temperature range and under mechanical stimulus. In addition, the H6L/Tb xerogel is also luminescent in aqueous solution. UV-vis and FT-IR spectroscopy and XRD studies reveal that the stable luminescence of the H6L/Tb gel depends on heat-set-induced strong hydrogen bonding, π-π stacking, and metal-ligand interactions. This study provides a heat-set approach to the preparation of luminescence-stable metallogel materials, such metallogels are potentially useful in anti-counterfeiting and sensing fields, among others.

Reversible Redox Switching of Concurrent Luminescence and Visual Color Change Based on Lanthanide Metallogel.

The development of reversible redox supramolecular gels capable of concurrent luminescence switch and visible color change with the facile redox process has always been an intriguing challenge. A redox-responsive supramolecular lanthanide metallogel with strong luminescence and yellow color is obtained via coordination interaction between 3,5-dinitrosalicylic acid (DNSA) and europium (Eu3+). Upon the addition of TiO2 to the prepared gel (DNSA/Eu3+ gel), the oxidation process of the gel (DNSA/Eu3+/TiO2 gel) can be easily achieved by UV irradiation. The DNSA/Eu3+/TiO2 gel exhibits a concurrent reversible "on-off" luminescence and color change in response to redox stimuli. The DNSA/Eu3+/TiO2 gel shows a concurrent quench of luminescence and a color change from yellow to red when the gel was stimulated by the reductant. Upon UV irradiation, the luminescence and color of the reduced DNSA/Eu3+/TiO2 gel restored to its initial state due to the strong oxidation ability of hydroxyl radicals derived from photocatalytic oxidation of TiO2. The results of UV-vis and mass spectroscopy indicated that the reversible redox responsiveness of DNSA/Eu3+/TiO2 gel depends on the reversible oxidation-reduction reactions of DNSA. Moreover, DNSA/Eu3+/TiO2 gel remains stable because the morphology of the gel had no change during the redox process. Exemplarily, the application of DNSA/Eu3+/TiO2 gels to achieve luminescent patterning was investigated. The results demonstrated that the prepared metallogel has potential applications in the fields of writable materials, anticounterfeiting, sensors, and others.

Improved photocatalytic degradation of perfluorooctanoic acid on oxygen vacancies-tunable bismuth oxychloride nanosheets prepared by a facile hydrolysis.

Oxygen vacancies (OVs) defective BiOCl nanosheets are important for developing efficient hole (h+) oxidation. Herein, a facile hydrolysis without the use of organic solvent was developed for preparing OVs-controllable BiOCl nanosheets, which was then applied to degrade perfluorooctanoic acid (PFOA), a typical persistent organic pollutant, which is resistance to the oxidation by hydroxyl radicals (OH). As changing the alkali source in the preparation process, the ratio of OVs in BiOCl nanosheets increases from 0.573 to 0.981, and the photocatalytic performance of BiOCl for the degradation and defluorination of PFOA increases by 3-4 times. A linear relationship between the photocatalytic degradation of PFOA and the OVs amount in BiOCl was observed. The introduction of OVs in BiOCl not only offers localized states for trapping photo-generated electrons, but also acts as active sites for adsorbing PFOA, both of which are helpful to improve the h+-oxidation of PFOA. The photocatalytic degradation of PFOA was more effective at pH 4.6 compared to other previously reported highly acidic and alkaline conditions. These factors ultimately guaranteed the improved degradation and defluorination of PFOA over OVs-rich BiOCl nanosheets. This work provides a readily achievable tactic to induce OVs formation on nanocrystals for enhanced photocatalytic water treatment.

Al3+ enhanced room temperature phosphorescence of Pd-porphyrin resided in hybrid supramolecular gels and used for detection of trace Hg2+ ions.

Micelle-hybridized supramolecular hydrogels were constructed through the self-assembly of gelator N,N-dibenzoyl-L-cystine (DBC) and micelles formed from a Gemini surfactant (G12-8-12). A phosphor, palladium meso-tetra (4-carboxyphenyl) porphyrin (Pd-TCPP) and Al3+ ions were loaded within the hybrid system. Interestingly, the room temperature phosphorescence (RTP) of Pd-TCPP can be efficiently enhanced and modulated by the concentration of Al3+ ions. The enhancement effect could be attributed to the interactions between Al3+ and DBC as well as porphyrin, which verified by 1H NMR analysis. The study of transmission electron microscopy and scanning electron microscopy indicated that a more compact 3D network structure of the gel system was formed upon the addition of Al3+. In addition, measurement of critical micelle concentration indicated that Al3+ ions increase the surface activity of G12-8-12 to promote micelle formation, thereby increasing the dispersion of Pd-TCPP in the hybrid gels. Based on the synergistic effect of these results, the non-radiative transition of Pd-TCPP was efficiently inhibited, resulting in highly efficient RTP. Furthermore, the enhanced RTP of as-prepared gel system shows potential application to detect trace Hg2+ ions because the RTP can be quenched by Hg2+. A linear relationship between RTP against the logarithmic concentration of Hg2+ was found over the range of 6 × 10-8 and 1 × 10-6 mol/L. The detection limit was found to be 0.017 nmol/L.

Decomposition of Sulfonyl Azide Isocyanate and Sulfonyl Diazide: The Oxygen-Shifted Curtius Rearrangement via Sulfonyl Nitrenes.

Sulfonyl azide isocyanate, (OCN)S(O)2N3, was prepared and characterized by IR (gas, matrix-isolation), Raman (liquid), and UV-vis spectroscopy. Upon flash vacuum pyrolysis (FVP) at ca. 1000 K, gaseous (OCN)S(O)2N3 decomposes completely and yields fragments N2, SO2, SO3, NCN, N3, NCO, CO, CN, and NO. In contrast, the azide splits off N2 and furnishes a transient triplet sulfonyl nitrene intermediate (OCN)S(O)2N upon a 266 nm laser irradiation in solid Ne-matrix at 2.8 K. Subsequent photolysis of the nitrene with visible light (λ = 380-450 nm) results in oxygen-shifted Curtius rearrangement to a novel nitroso sulfoxide (OCN)S(O)NO. For comparison, the photodecomposition of the closely related sulfonyl diazide O2S(N3)2 in a solid Ar matrix was also studied. Upon an ArF excimer laser (193 nm) photolysis, O2S(N3)2 decomposes and yields N2, SO2, and OSNNO via the intermediacy of an elusive sufonyl nitrene N3S(O)2N. Further visible light irradiation (λ > 395 nm) leads to depletion of N3S(O)2N and OSNNO and concomitant formation of SO2 and N2. The identification of the intermediates in cryogenic matrixes by IR spectroscopy was supported by 15N-labeling experiments and quantum chemical calculations. The mechanism for the decomposition of both sulfonyl azides (OCN)S(O)2N3 and O2S(N3)2 was discussed on the basis of the observed intermediates and the calculated potential energy profiles.